Dissociative intramolecular charge transfer after local two-photon ionization of ferrocene derivatives with aromatic chromophores

Experimental evidence for dissociative intramolecular charge transfer proce sses is found for gas-phase ferrocene-aniline derivatives after local ioniz ation at the aniline chromophore site via intermediate states with predomin ant aniline character. The direct ionization at the ferrocene site can be e xcluded since there is a rapid dissociation of ferrocene in the intermediat e state prior to ionization so that no ferrocene ions would be produced in this case. Because of the higher local ionization energy of the chromophore , charge transfer takes place after local ionization. The released energy a nd additional photon absorption leads to breaking of bonds and results in a dissociation into intact ferrocene or ferrocene-containing cations and neu tral fragments.